KR102375983B1 - Materials for electronic devices - Google Patents

Abstract

The present invention relates to a heterospirobifluorene compound, a method for preparing the same, and an electronic device, particularly an organic electroluminescent device comprising the heterospirobifluorene derivative.

Description

Materials for electronic devices {MATERIALS FOR ELECTRONIC DEVICES}

The present application relates to heterospirobifluorene compounds of formula (I) as defined in detail below. The compounds are preferably used in electronic devices, particularly preferably in organic electroluminescent devices (OLEDs).

An electronic device in the meaning of the present application means a so-called organic electronic device including an organic semiconductor material as a functional material. In particular, they mean OLED.

The structures of OLEDs in which organic compounds are used as functional materials are described, for example, in US 4539507, US 5151629, EP 0676461 and WO 98/27136. In general, the term OLED means an electronic device comprising at least one layer comprising an organic compound and emitting light upon application of an electrical voltage.

A layer having a hole-transporting function (hole-transporting layer), for example, a hole-injecting layer, a hole-transporting layer, an electron-blocking layer and an emitting layer, has a great influence on the performance data of the electron count.

It is known in the prior art to use triarylamines as materials having hole-transporting properties in the aforementioned layers. These are monotriarylamines (eg as described in JP 1995/053955, WO 2006/123667 and JP 2010/222268), or bis- or other oligoamines (eg as described in US 7504163 or US 2005/0184657) same) can be. Known examples of triarylamine compounds as materials having hole-aqueous properties for OLEDs are, inter alia, tris-p-biphenylamine, N,N′-di-1-naphthyl-N,N′-diphenyl -1,1'-biphenyl-4,4'-diamine (NPB) and 4,4',4''-tris-(3-methylphenylphenylamino)triphenylamine (MTDATA).

It is known from the prior art, for example from WO 2012/150001, to use acridine derivatives in OLEDs. However, no spirobisacridine derivatives are presented in this published specification.

In addition, the prior art, for example JP 2002-265938, discloses the use of spirobisacridine compounds in OLEDs. The compounds described in these published specifications contain no substituents on the benzene ring of the spirobisacridine backbone or contain a phenyl group on the nitrogen atom of the spirobisacridine backbone.

A further published specification describing the use of spirobisacridine compounds in OLEDs is KR 2011-0120075. The compounds described in these published specifications contain no substituents on the benzene ring of the spirobisacridine backbone.

Although the compounds disclosed in the aforementioned documents are well suited for use in electronic devices, there continues to be a need for new compounds for this use. In particular, there is a need for compounds that result in improvements in performance data of electronic devices, particularly in lifetime, efficiency and operating voltage. New materials with corresponding properties are constantly being searched for, especially for use in hole-transporting layers of electronic devices.

During the search for novel materials for this use, surprisingly, they conform to the formula (I) defined below and in particular they have an aromatic or heteroaromatic system extended at one or more nitrogen atoms and are aromatic at at least one of the benzene rings of the spirobisacridine backbone. Or it has now been found that spirobisacridine compounds characterized as having a heteroaromatic ring system are very suitable for use in OLEDs. They are particularly suitable for use in hole-transporting layers.

The compound found has at least one property selected from very good hole-conducting properties, very good electron-blocking properties, high oxidation stability, good solubility and high temperature stability. When used in OLEDs, they result in one or more advantageous properties of OLEDs being selected from long lifetimes, high quantum efficiencies and low operating voltages.

The present invention relates to compounds of formula (I):

[wherein the following applies to the symbols and exponents used:

A is C or Si;

Y is at each occurrence, identically or differently, N or P;

X is at each occurrence, identically or differently, CR ¹ or N;

Ar ¹ , Ar ² in each case, identically or differently, are aromatic ring systems having 6 to 40 aromatic ring atoms, which may be substituted by one or more radicals R ² , or 5 to 40 aromatic ring atoms heteroaromatic ring system, which may be substituted by one or more radicals R ² ;

Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ in each case, identically or differently, are aromatic ring systems having 6 to 40 aromatic ring atoms, which may be substituted by one or more radicals R ² , or 5 to 40 heteroaromatic ring systems having two aromatic ring atoms, which may be substituted by one or more radicals R ² ;

R ¹ , R ² in each occurrence, identically or differently, is H, D, F, C(=O)R ³ , CF ₃ , OCF ₃ , CN, Si(R ³ ) ₃ , N(R ³ ) ₂ , P(=O)(R ³ ) ₂ , OR ³ , S(=O)R ³ , S(=O) ₂ R ³ , straight chain alkyl or alkoxy group having 1 to 20 C atoms, 3 to 20 C branched or cyclic alkyl or alkoxy groups with atoms, alkenyl or alkynyl groups with 2 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms and hetero with 5 to 40 aromatic ring atoms selected from aromatic ring systems; wherein two or more radicals R ¹ or R ² may be linked to each other and may form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring system and heteroaromatic ring system may each be substituted by one or more radicals R ³ ; wherein one or more CH ₂ groups in said alkyl, alkoxy, alkenyl and alkynyl groups are -R ³ C=CR ³ -, -C≡C-, Si(R ³ ) ₂ , C=O, C=NR ³ , - C(=O)O-, -C(=O)NR ³ -, NR ³ , P(=O)(R ³ ), -O-, -S-, SO or SO ₂ ;

R ³ is at each occurrence, identically or differently, H, D, F, C(=O)R ⁴ , CF ₃ , OCF ₃ , CN, Si(R ⁴ ) ₃ , N(R ⁴ ) ₂ , P(= O)(R ⁴ ) ₂ , OR ⁴ , S(=O)R ⁴ , S(=O) ₂ R ⁴ , straight chain alkyl or alkoxy group having 1 to 20 C atoms, having 3 to 20 C atoms branched or cyclic alkyl or alkoxy groups, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms is selected from; wherein two or more radicals R ³ may be linked to each other and may form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring system and heteroaromatic ring system may each be substituted by one or more radicals R ⁴ ; One or more CH ₂ groups in said alkyl, alkoxy, alkenyl and alkynyl groups are -R ⁴ C=CR ⁴ -, -C≡C-, Si(R ⁴ ) ₂ , C=O, C=NR ⁴ , -C (=O)O-, -C(=O)NR ⁴ -, NR ⁴ , P(=O)(R ⁴ ), -O-, -S-, SO or SO ₂ ;

R ⁴ in each occurrence, identically or differently, represents H, D, F, CN, an alkyl group having 1 to 20 C atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and 5 to 40 aromatic ring atoms selected from heteroaromatic ring systems having; wherein two or more radicals R ⁴ may be linked to each other and may form a ring; wherein the alkyl group, aromatic ring system and heteroaromatic ring system may be substituted with F or CN;

a, b, c, d are at each occurrence, identically or differently, 0 or 1;

At least one of the two groups Ar ¹ and Ar ² is an aromatic ring system having 12 to 40 aromatic ring atoms, which may be substituted by one or more radicals R ² , or heteroaromatic having 12 to 40 aromatic ring atoms is a ring system, which may be substituted by one or more radicals R ² ;

at least one of the indices a, b, c and d is 1].

If the index a, b, c or d is zero, then the corresponding group Ar ³ , Ar ⁴ , Ar ⁵ or Ar ⁶ is absent.

When the index a, b, c or d is 1, the corresponding group Ar ³ , Ar ⁴ , Ar ⁵ or Ar ⁶ is bonded to one of the groups X of the ring. This group X is identical to C (corresponding to carbon tetravalent).

An aryl group in the sense of the present invention contains 6 to 60 aromatic ring atoms, none of which are heteroatoms. An aryl group in the meaning of the present invention is intended to mean a simple aromatic ring, ie benzene, or a condensed aromatic polycyclic ring system, for example naphthalene, phenanthrene or anthracene. A condensed aromatic polycyclic ring system in the meaning of the present application consists of two or more simple aromatic rings condensed with each other. Condensation between rings means that the rings share one or more edges with each other.

A heteroaryl group in the sense of the present invention contains 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom of the heteroaryl group is preferably selected from N, O and S. A heteroaryl group in the sense of the present invention means a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, for example pyridine, pyrimidine or thiophene, or a condensed heteroaromatic polycyclic ring system, for example quinoline or carbazole do. A condensed heteroaromatic polycyclic ring system in the meaning of the present application consists of two or more simple heteroaromatic rings condensed with each other. Condensation between rings means that the rings share one or more edges with each other.

An aryl or heteroaryl group which in each case may be substituted by the above-mentioned radicals and which may be connected to the aromatic or heteroaromatic ring system via any desired position is in particular benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene , chrysene, perylene, triphenylene, fluoroantene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, iso Benzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, Benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthymidazole, phenantrimidazole, pyridimidazole, pyrazinimidazole, quinoxaline Midazole, oxazole, benzoxazole, naphtoxazole, antroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyri midine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole , 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole , 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1 ,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, groups derived from indolizine and benzothiadiazole.

An aromatic ring system in the sense of the present invention contains 6 to 60 C atoms in the ring system and contains no heteroatoms as aromatic ring atoms. Accordingly, an aromatic ring system in the sense of the present invention does not contain a heteroaryl group. An aromatic ring system in the sense of the present invention does not necessarily contain only aryl groups, but instead a plurality of additional aryl groups are single bonds or non-aromatic units, for example one or more optionally substituted C, Si, N, O or S It is intended to mean a system that can be linked by atoms. The non-aromatic units preferably contain less than 10% of atoms other than H, based on the total number of atoms other than H in the system. Thus, for example, systems such as 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ether and stilbene also have two or more aryl groups in the sense of the present invention. For example, it is intended to be an aromatic ring system, a system connected by linear or cyclic alkyl, alkenyl or alkynyl groups or silyl groups. In addition, systems in which two or more aryl groups are linked to each other via a single bond are also intended in the sense of the present invention to be aromatic ring systems, such as biphenyl and terphenyl.

A heteroaromatic ring system in the sense of the present invention contains 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms of the heteroaromatic ring system are preferably selected from N, O and/or S. A heteroaromatic ring system corresponds to the above-mentioned definition of an aromatic ring system, but contains one or more heteroatoms as one of the aromatic ring atoms. It therefore differs from an aromatic ring system (which cannot contain a heteroatom as an aromatic ring atom according to the definition above) in the meaning of the definition of the present application.

An aromatic ring system having 6 to 60 aromatic ring atoms or a heteroaromatic ring system having 5 to 60 aromatic ring atoms is, in particular, the groups mentioned above under the aryl group and heteroaryl group, and biphenyl, terphenyl, quarterphenyl , fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, truxene, isotruxene, spirotruxen, spiroisotruxen, indenocarbazole, or a group thereof means a group derived from a combination of

For the purposes of the present invention, a straight chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms (also wherein The individual H atoms or CH ₂ groups may be substituted by the groups mentioned above under the definition of radicals), preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl , t-butyl, 2-methyl-butyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2 -Ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl , cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl.

An alkoxy or thioalkyl group having 1 to 40 C atoms, also wherein an individual H atom or a CH ₂ group may be substituted by the groups mentioned above in the definition of a radical, is preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n -Hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroe Toxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n- Hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-tri Fluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cycloox tenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

Formulations in which two or more radicals can form a ring with each other are intended for the purposes of the present application to mean, inter alia, in which the two radicals are linked to each other by a chemical bond. However, the formulations mentioned above are also intended to mean that when one of the two radicals represents hydrogen, the second radical bonds at the position where the hydrogen atom binds, forming a ring.

According to a preferred embodiment, the compounds of formula (I) do not contain arylamino groups as substituents. An arylamino group in the meaning of the present application means a group in which one or more aryl or heteroaryl groups, preferably three aryl or heteroaryl groups, are bonded to a nitrogen atom.

According to a further preferred embodiment of the invention, the compounds of formula (I) do not contain fused aryl groups having more than 10 aromatic ring atoms and do not contain fused heteroaryl groups having more than 14 aromatic ring atoms .

Preferably, exactly 1, 2 or 3 indices selected from the indices a, b, c and d are equal to 1, particularly preferably exactly 1 or 2 indices selected from the indices a, b, c and d is equal to 1.

According to a preferred embodiment of the invention, the indices a is equal to 1 and the indices b, c and d are equal to zero.

According to an alternative preferred embodiment, the indices a and b are equal to 1 and the indices c and d are equal to 0.

According to an alternative preferred embodiment, the indices a and c are equal to 1 and the indices b and d are equal to 0.

A is preferably a carbon atom.

Y is preferably a nitrogen atom.

Preferably at most 3 groups X, particularly preferably at most 2 groups X, very particularly preferably at most 1 group X, per 6-membered ring in the compound of formula (I) are identical to N.

Preferably, up to two directly adjacent groups X in the ring are identical to N.

X is preferably equal to CR ¹ .

Ar ¹ and Ar ² are preferably, identically or differently in each case, an aromatic ring system having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R ² , or 5 to 24 aromatic rings heteroaromatic ring systems having atoms, which may be substituted by one or more radicals R ² . Thus, in combination therewith, an aromatic ring system in which at least one of the two groups Ar ¹ and Ar ² has 12 to 24 aromatic ring atoms, which may be substituted by one or more radicals R ² , or 12 to 24 aromatic ring atoms It is preferably a heteroaromatic ring system with , which may be substituted by one or more radicals R ² . Particularly preferably, aromatic ring systems in which both of the groups Ar ¹ and Ar ² in each case, identically or differently, have from 12 to 24 aromatic ring atoms, which may be substituted by one or more radicals R ² , and heteroaromatic ring systems having 12 to 24 aromatic ring atoms, which may be substituted by one or more radicals R ² .

Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each preferably benzene, naphthalene, phenanthrene, fluoroantene, biphenyl, terphenyl, quaterphenyl, fluorene, indenofluorene, spiro Bifluorene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, indole, isoindole, carbazole, indolocarbazole, indenocar at least one group selected from bazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzimidazole, pyrimidine, pyrazine and triazine, wherein each group is to be substituted by at least one radical R ² can

Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ are preferably, identically or differently in each case, an aromatic ring system having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R ² , or heteroaromatic ring systems having 5 to 24 aromatic ring atoms, which may be substituted by one or more radicals R ² .

The groups Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ appearing in the compound of formula (I) are preferably selected identically.

Preferred embodiments of the groups Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are the groups indicated below:

Here, the indicated groups may each be substituted by the radical R ² at one or more of the free positions, and the bond indicated by * indicates the bond position of each group.

Preferably, at least one of the groups Ar ¹ and Ar ² is selected from one of the aforementioned groups of the formulas (Ar-2) to (Ar-15) and (Ar-18) to (Ar-66). Particularly preferably, both the groups Ar ¹ and Ar ² are selected from one of the aforementioned groups of the formulas (Ar-2) to (Ar-15) and (Ar-18) to (Ar-66).

Preferably, at least one of the groups Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ comprises at least one heteroaryl group as defined above. The at least one heteroaryl group preferably has 5 to 20 aromatic ring atoms, particularly preferably 6 to 14 aromatic ring atoms.

The radical R ¹ is preferably in each case, identically or differently, H, D, F, CN, Si(R ³ ) ₃ , a straight-chain alkyl or alkoxy group having 1 to 10 C atoms, 3 to 10 C atoms a branched or cyclic alkyl or alkoxy group having an aromatic ring system having 6 to 24 aromatic ring atoms and a heteroaromatic ring system having 5 to 24 aromatic ring atoms; wherein the alkyl and alkoxy groups, the aromatic ring system and the heteroaromatic ring system may each be substituted by one or more radicals R ³ ; At least one CH ₂ group in the alkyl or alkoxy group is -C≡C-, -R ³ C=CR ³ -, Si(R ³ ) ₂ , C=O, C=NR ³ , -NR ³ -, -O -, -S-, -C(=O)O- or -C(=O)NR ³ - . The radical R ¹ is particularly preferably in each case identically or differently H, F, CN, Si(R ³ ) ₃ , an aromatic ring system having 6 to 24 aromatic ring atoms and 5 to 24 aromatic ring atoms selected from heteroaromatic ring systems having; wherein the aromatic ring system and the heteroaromatic ring system may each be substituted by one or more radicals R ³ . The radical R ¹ is very particularly preferably identical to H.

The radical R ² is preferably in each case, identically or differently, H, D, F, CN, Si(R ³ ) ₃ , a straight-chain alkyl or alkoxy group having 1 to 10 C atoms, 3 to 10 C atoms a branched or cyclic alkyl or alkoxy group having an aromatic ring system having 6 to 24 aromatic ring atoms and a heteroaromatic ring system having 5 to 24 aromatic ring atoms; wherein the alkyl and alkoxy groups, the aromatic ring system and the heteroaromatic ring system may each be substituted by one or more radicals R ³ ; At least one CH ₂ group in the alkyl or alkoxy group is -C≡C-, -R ³ C=CR ³ -, Si(R ³ ) ₂ , C=O, C=NR ³ , -NR ³ -, -O -, -S-, -C(=O)O- or -C(=O)NR ³ - . The radical R ² is particularly preferably in each case identically or differently H, F, CN, Si(R ³ ) ₃ , a straight-chain alkyl group having 1 to 10 C atoms, branched having 3 to 10 C atoms or a cyclic alkyl group, an aromatic ring system having 6 to 24 aromatic ring atoms and a heteroaromatic ring system having 5 to 24 aromatic ring atoms; Here, the alkyl group, the aromatic ring system and the heteroaromatic ring system may each be substituted by one or more radicals R ³ .

The radical R ³ is preferably in each case, identically or differently, H, D, F, CN, Si(R ⁴ ) ₃ , a straight-chain alkyl or alkoxy group having 1 to 10 C atoms, 3 to 10 C atoms a branched or cyclic alkyl or alkoxy group having an aromatic ring system having 6 to 24 aromatic ring atoms and a heteroaromatic ring system having 5 to 24 aromatic ring atoms; wherein the alkyl and alkoxy groups, the aromatic ring system and the heteroaromatic ring system may each be substituted by one or more radicals R ⁴ ; At least one CH ₂ group in the alkyl or alkoxy group is -C≡C-, -R ⁴ C=CR ⁴ -, Si(R ⁴ ) ₂ , C=O, C=NR ⁴ , -NR ⁴ -, -O -, -S-, -C(=O)O- or -C(=O)NR ⁴ - . The radicals R ³ are particularly preferably in each case identically or differently H, F, CN, Si(R ⁴ ) ₃ , straight-chain alkyl groups with 1 to 10 C atoms, branched with 3 to 10 C atoms or a cyclic alkyl group, an aromatic ring system having 6 to 24 aromatic ring atoms and a heteroaromatic ring system having 5 to 24 aromatic ring atoms; Here, the alkyl group, the aromatic ring system and the heteroaromatic ring system may each be substituted by one or more radicals R ⁴ .

The compound of formula (I) preferably conforms to one of the following formulas (I-1) to (I-3):

Here, the appearing symbols and exponents are defined as above.

In particular, in the formulas (I-1) to (I-3) wherein X is equal to CR ¹ , and precisely 1, precisely 2 or exactly 3 indices selected from the indices a, b, c and d are 1. compounds are preferred.

Of the formulas (I-1) to (I-3), the formula (I-1) is preferable.

The compounds of formula (I) particularly preferably conform to one of the following formulas (I-1-1) to (I-1-4):

Here, the appearing symbol is defined as above.

Combination of preferred embodiments of formulas (I-1-1) to (I-1-4) with the aforementioned preferred embodiments of groups R ¹ , Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ This is particularly preferred.

Examples of compounds of formula (I) are given in the table below:

Compounds of formula (I) can be prepared using known reactions of organic chemistry, for example using bromination reactions, Buchwald coupling reactions and Suzuki coupling reactions.

Preferred processes for the preparation of compounds of formula (I) are shown and described in the following general terms. In the schemes, the compounds shown may be optionally substituted. An explicit example of the method is shown in the working example.

A preferred process for the preparation of compounds of formula (I) starts with acridinone or a derivative of acridinone (Scheme 1). This is reacted in a Buchwald coupling, where an acridinone substituted by an aryl group on N is obtained. It is brominated in a further step, and the aryl group is introduced at the brominated position in the Suzuki reaction. This route preferably provides a symmetric acridinone intermediate.

Scheme 1

Asymmetric acridinone basic structures can be prepared according to Scheme 2. For this, the starting material is a diphenylamine derivative, which is converted into a carboxyl-substituted triphenyl derivative. It can be converted to an asymmetrically substituted acridinone derivative in a ring closure reaction.

Scheme 2

Symmetrically substituted or asymmetrically substituted acridinone derivatives are reacted with appropriately substituted diphenylamines to yield spirobisacridine (Scheme 3). The reaction leading to the formation of the spiro unit may be followed by a Suzuki coupling reaction for introduction of a substituent into the aromatic ring and/or a Buchwald coupling reaction for introduction of a substituent on the nitrogen atom of the spirobisacridine. .

Scheme 3

The synthetic methods described are only preferred methods. Alternative methods are possible, if necessary, upon which the person skilled in the art can rely in the context of his general expertise.

The present invention relates to a process for the preparation of compounds of formula (I), characterized in that it comprises the steps of:

1) reacting a halogen-substituted diphenylamine derivative with an acridinone derivative in the presence of an organometallic compound;

2) yielding a spirobisacridine derivative by ring closure reaction of the intermediate formed in 1);

3) introducing an aryl or heteroaryl group on the free nitrogen atom of the spirobisacridine derivative by Buchwald coupling.

Step 2) is preferably carried out after step 1), and step 3) is preferably carried out after step 2). In addition, derivatization and coupling reactions, for example Suzuki couplings, preferably follow step 3). It is also preferred again that the organometallic compound in step 1) is an organolithium base, particularly preferably n-butyllithium. It is also preferred that a nucleophilic addition reaction to the carbonyl group, in which a tertiary alcohol is formed, is carried out in step 1).

The compounds described above, in particular compounds substituted by reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic acid esters, can be used as monomers for the preparation of the corresponding oligomers, dendrimers or polymers. Suitable reactive leaving groups are, for example, bromine, iodine, chlorine, boronic acid, boronic acid esters, amines, alkenyl or alkynyl groups (with a terminal C-C double bond or C-C triple bond), oxirane, oxetane, cycloaddition, e.g. for example groups that undergo 1,3-polar cycloaddition, such as dienes or azides, carboxylic acid derivatives, alcohols and silanes.

Accordingly, the present invention also relates to oligomers, polymers or dendrimers comprising at least one compound of formula (I), wherein the bond(s) to the polymer, oligomer or dendrimer is substituted by R ¹ or R ² ( It can be localized at any desired location in I). Depending on the linkage of the compound of formula (I), said compound is a side chain component or a main chain component of an oligomer or polymer. In the meaning of the present invention, an oligomer means a compound which is constructed from three or more monomer units. In the sense of the present invention, a polymer means a compound which is built up from ten or more monomer units. The polymers, oligomers or dendrimers according to the invention may be conjugated, partially conjugated or non-conjugated. The oligomers or polymers according to the invention may be linear, branched or resinous. In structures linked in a linear manner, the units of formula (I) may be directly linked to each other, or via a divalent group, for example via a substituted or unsubstituted alkylene group, via a heteroatom, or a divalent aromatic or heteroaromatic group can be connected to each other through In branched and dendritic structures, for example, three or more units of formula (I) are linked via a trivalent or polyvalent group, for example via a trivalent or polyvalent aromatic or heteroaromatic group to form a branched or resinous oligomer or polymers can be formed.

The same preferences as described above for the compounds of the formula (I) apply to the repeating units of the formula (I) in oligomers, dendrimers and polymers.

For the preparation of oligomers or polymers, the monomers according to the invention are copolymerized or homopolymerized with further monomers. Suitable and preferred comonomers are fluorene (eg according to EP 842208 or WO 2000/22026), spirobifluorene (eg according to EP 707020, EP 894107 or WO 2006/061181), paraphenylene (eg according to EP 707020, EP 894107 or WO 2006/061181) For example according to WO 1992/18552), carbazole (for example according to WO 2004/070772 or WO 2004/113468), thiophene (for example according to EP 1028136), dihydrophenanthrene (for example according to WO 2004/070772 or according to WO 2004/113468) 2005/014689 or according to WO 2007/006383), cis- and trans-indenofluorenes (eg according to WO 2004/041901 or WO 2004/113412), ketones (eg according to WO 2005/040302) , phenanthrene (eg according to WO 2005/104264 or WO 2007/017066) or also a plurality of these units. Polymers, oligomers and dendrimers usually contain additional units, for example emitting (fluorescent or phosphorescent) units, for example vinyltriarylamine (eg according to WO 2007/068325) or phosphorescent metal complexes (eg according to WO 2006/068325). /003000) and/or charge-transport units, in particular those based on triarylamines.

The polymers and oligomers according to the invention are generally prepared by polymerization of at least one type of monomer, of which at least one monomer results in repeating units of the formula (I) in the polymer. Suitable polymerization reactions are known to the person skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions resulting in C-C or C-N linkages are

(A) SUZUKI polymerization;

(B) Yamamoto polymerization;

(C) STILLE polymerization; and

(D) HARTWIG-BUCHWALD polymerization.

The manner in which polymerization can be carried out by this method and in which the polymer can then be separated and purified from the reaction medium is known to the person skilled in the art and is available in the literature, for example WO 2003/048225, WO 2004/037887 and WO 2004/037887 is described in detail in

For the processing of the compounds according to the invention from the liquid phase, for example by spin coating or printing methods, formulations of the compounds according to the invention are necessary. These formulations may be, for example, solutions, dispersions or emulsions. It may be preferable to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, Dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-phenchon, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2 -Methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α -Terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, pe Nethol, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tri propylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptyl-benzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane or mixtures of these solvents. .

The present invention therefore also relates to a formulation comprising at least one compound of formula (I), or at least one polymer, oligomer or dendrimer containing at least one unit of formula (I), and at least one solvent, preferably an organic solvent, It relates in particular to solutions, dispersions or emulsions. The manner in which solutions of this type can be prepared are known to the person skilled in the art and are described, for example, in WO 2002/072714, WO 2003/019694 and citations thereof.

The compounds according to the invention are suitable for use in electronic devices, in particular organic electroluminescent devices (OLEDs). Depending on the substitution, the compounds are used in different functions and layers.

The invention therefore also relates to the use of a compound of the formula (I) in an electronic device and to an electronic device comprising at least one compound of the formula (I). The electronic device is preferably an organic integrated circuit (OIC), an organic field effect transistor (OFET), an organic thin film transistor (OTFT), an organic light emitting transistor (OLET), an organic solar cell (OSC), an organic optical detector, an organic photoreceptor, organic electroluminescent devices (OFQDs), organic light emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and particularly preferably organic electroluminescent devices (OLEDs).

The invention also relates, as already mentioned above, to an electronic device comprising at least one compound of the formula (I). In this case, the electronic device is preferably selected from the above-mentioned devices.

Particular preference is given to organic electroluminescent devices (OLEDs) comprising an anode, a cathode and at least one emissive layer, wherein at least one organic layer, which may be an emissive layer, a hole-transporting layer or another layer, comprises at least one compound of formula (I) characterized by including.

Besides the cathode, anode and emissive layers, the organic electroluminescent device may also comprise further layers. These are, for example, in each case one or more of a hole-injection layer, a hole-transport layer, a hole-blocking layer, an electron-transport layer, an electron-injection layer, an electron-blocking layer, an excitation-blocking layer, an interlayer, a charge-generating layer. (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsu-moto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer ) and/or organic or inorganic p/n junctions.

The layer sequence of the organic electroluminescent device comprising the compound of formula (I) is preferably as follows:

anode / hole-injecting layer / hole-transporting layer / optionally further hole-transporting layer / optionally electron-blocking layer / emissive layer / electron-transporting layer / electron-injecting layer / cathode.

However, it is not necessary for all of the above layers to be present, and additional layers may additionally be present.

The organic electroluminescent device according to the invention may also comprise a plurality of emitting layers. These emissive layers in this case particularly preferably have a sum of a plurality of emission maxima of 380 nm to 750 nm, which results in white emission as a whole, i.e. which can be fluorescent or phosphorescent and which emits blue or yellow or orange or red light. A variety of emitting compounds are used in the emitting layer. Particular preference is given to a three-layer system, ie a system having three emitting layers, wherein the three layers exhibit blue, green and orange or red radiation (for the basic structure, see, for example, WO 2005/011013). The compound according to the invention is preferably present in a hole-transport layer, a hole-injection layer or an electron-blocking layer.

It is preferred according to the invention that the compounds of formula (I) are used in electronic devices comprising at least one phosphorescent emitting compound. The compound here may be present in various layers, preferably in a hole-transporting layer, an electron-blocking layer, a hole-injecting layer or an emissive layer.

The term phosphorescent emitting compound generally includes compounds in which luminescence occurs by a spin-forbidden transition, eg, a transition from an excited triplet state or a state having a high spin quantum number, eg, a quadruplet state.

In particular, suitable phosphorescent emitting compounds (= triplet emitters) are preferably compounds emitting suitable excitation in the visible region, and also contain more than 20, preferably more than 38 and less than 84, particularly preferably more than 56 and less than 80 It contains one or more atoms having an atomic number. The phosphorescent compounds used are preferably compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium, platinum or copper .

For the purposes of the present invention, all luminescent iridium, platinum or copper complexes are regarded as phosphorescent emitting compounds.

Examples of radioactive compounds described above are in applications WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373 and US 2005/ 0258742. In general, all phosphorescent complexes as used according to the prior art for phosphorescent OLEDs and known to the person skilled in the art in the field of organic electroluminescent devices are suitable. The person skilled in the art will also be able to utilize further phosphorescent complexes without inventive step in combination with the compounds of formula (I) in organic electroluminescent devices. Further examples are shown in the table below.

However, the compounds of formula (I) can also be used according to the invention in electronic devices comprising at least one luminescent emitting compound.

In a preferred embodiment of the present invention, the compound of formula (I) is used as hole-transporting material. The compound is preferably present in a hole-transporting layer, an electron-blocking layer or a hole-injecting layer.

The hole-transporting layer according to the present application is a layer having a hole-transporting function located between the anode and the emission layer.

A hole-injecting layer and an electron-blocking layer in the sense of the present invention are intended to be specific embodiments of a hole-transporting layer. When a plurality of hole-transporting layers are present between the anode and the emissive layer, the hole-injecting layer is a hole-transporting layer directly adjacent to or separated only from the anode by a single coating of the anode. When a plurality of hole-transporting layers are present in the anode and the emissive layer, the electron-blocking layer is a hole-transporting layer directly adjacent to the emissive layer on the anode side.

When the compound of formula (I) is used as a hole-transporting material in a hole-transporting layer, hole-injecting layer or electron-blocking layer, the compound can be used as a pure material, i.e. in a hole-transporting layer in a proportion of 100% or , in combination with one or more additional compounds. According to a preferred embodiment, the organic layer comprising the compound of formula (I) further comprises at least one p-dopant. According to the invention, the p-dopant used is preferably an organic electron-accepting compound capable of oxidizing at least one of the other compounds of the mixture.

Particularly preferred embodiments of p-dopants are WO 2011/073149, EP 1968131, EP 2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, US 8044390, US 8057712, WO 2009/003455, WO 2010/094378, WO 2011 /120709, US 2010/0096600 and WO 2012/095143.

Particularly preferred p-dopants are quinodimethane compounds, azaindenofluorenediones, azaphenalenes, azatriphenylenes, I ₂ , metal halides, preferably transition metal halides, metal oxides, preferably one or more transition metals. or metal oxides containing metals of the third main group, and complexes with transition metal complexes, preferably Cu, Co, Ni, Pd and Pt with ligands containing at least one oxygen atom as the binding site. Dopants are also preferably transition metal oxides, preferably oxides of rhenium, molybdenum and tungsten, particularly preferably Re ₂ O ₇ MoO ₃ , WO ₃ and ReO ₃ .

The p-dopant is preferably distributed substantially uniformly in the p-doped layer. This can be done, for example, by co-evaporation of the p-dopant and hole-transporting material matrix.

Preferred p-dopants are in particular compounds:

In a further preferred embodiment of the present invention, as described in US 2007/0092755, the compounds of formula (I) are used as hole-transporting materials in combination with hexaazatriphenylene derivatives. The hexaazatriphenylene derivative is particularly preferably used in a separate layer.

In a further embodiment of the invention, the compounds of the formula (I) are used in the emitting layer as matrix material in combination with one or more emitting compounds, preferably phosphorescent emitting compounds.

The proportion of the matrix material in the emitting layer is in this case 50.0 to 99.9% by volume, preferably 80.0 to 99.5% by volume, particularly preferably 92.0 to 99.5% by volume for the fluorescent emitting layer, and 85.0 to 97.0 for the phosphorescent emitting layer volume %.

Correspondingly, the proportion of the emitting compound is from 0.1 to 50.0% by volume, preferably from 0.5 to 20.0% by volume, particularly preferably from 0.5 to 8.0% by volume for the fluorescent emitting layer, and from 3.0 to 15.0% by volume for the phosphorescent emitting layer. .

The emissive layer of the organic electroluminescent device may also comprise a system comprising a plurality of matrix materials (mixed-matrix systems) and/or a plurality of emissive compounds. Even in this case, the emitting compound is generally the compound whose proportion in the system is smaller, and the matrix material is the compound whose proportion in the system is greater. However, in individual cases, the proportion of individual matrix materials in the system may be smaller than the proportion of individual emitting compounds.

The compounds of formula (I) are preferably used as components of mixed-matrix systems. The mixed-matrix system preferably comprises two or three different matrix materials, particularly preferably two different matrix materials. One of the two materials is preferably a material having hole-transporting properties and the other material is a material having electron-transporting properties. The compound of formula (I) is preferably a matrix material having hole-transporting properties. However, the desired electron-transporting and hole-transporting properties of a mixed-matrix component can also be predominantly or completely combined in a single mixed-matrix component, where the additional mixed-matrix component(s) fulfill another function. The two different matrix materials are in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1, very particularly preferably 1:4 to 1:1. may exist as rain. Mixed-matrix systems are preferably used in phosphorescent organic electroluminescent devices. More precise information on mixed-matrix systems is provided inter alia in application WO 2010/108579.

A mixed-matrix system may comprise at least one emitting compound, preferably at least one phosphorescent emitting compound. In general, mixed-matrix systems are preferably used in phosphorescent organic electroluminescent devices.

Particularly suitable matrix materials that can be used as matrix components of mixed-matrix systems in combination with the compounds according to the invention are preferred matrix materials for the phosphorescent emitting compounds shown below, depending on what type of emitting compound is used in the mixed-matrix system. or preferred matrix materials for fluorescently emitting compounds.

Preferred phosphorescent emitting compounds for use in mixed-matrix systems are shown in the table below.

Preferred embodiments of various functional materials of electronic devices are shown below.

Preferred phosphorescent emitting compounds are the compounds mentioned above and the compounds shown in the table below:

Preferred fluorescently emitting compounds other than the compounds of formula (I) are selected from the class of arylamines. Arylamine or aromatic amine in the meaning of the present invention means a compound comprising three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a condensed ring system, particularly preferably a condensed ring system having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthracenamine, aromatic anthracenediamine, aromatic pyrenamine, aromatic pyrenediamine, aromatic chrysenamine or aromatic chrysenediamine. Aromatic anthraceneamine means a compound in which one diarylamino group is bonded directly to the anthracene group, preferably at the 9-position. Aromatic anthracenediamine means a compound in which two diarylamino groups are bonded directly to the anthracene group, preferably at the 9,10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously, wherein the diarylamino group is bonded to the pyrene, preferably at the 1-position or the 1,6-position. Further preferred emission compounds are indenofluorenamine or indenofluorenediamine (eg according to WO 2006/108497 or WO 2006/122630), benzoindenofluorenamine or benzoindenofluorenediamine (eg according to WO 2006/108497 or WO 2006/122630) according to WO 2008/006449), and dibenzoindenofluorenamine or dibenzoindenofluorenediamine (eg according to WO 2007/140847), and indo containing condensed aryl groups disclosed in WO 2010/012328 It is a nofluorene derivative. Likewise, the pyrenarylamines disclosed in WO 2012/048780 and those in WO 2013/185871 are preferred. Likewise, preference is given to the benzoindenofluorenamines disclosed in WO 2014/037077, the benzofluorenamines disclosed in WO 2014/106522 and the benzoindenofluorenes disclosed in WO 2014/111269.

Preferably suitable matrix materials for fluorescence emitting compounds are materials from various classes of materials. Preferred matrix materials are oligoarylenes (eg 2,2',7,7'-tetraphenylspirobifluorene or dinaphthylanthracene according to EP 676461), in particular oligoarylenes containing condensed aromatic groups, oligoaryl lenvinylene (eg DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes (eg according to WO 2004/081017), hole-conducting compounds (eg according to WO 2004/058911) according to), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides and the like (eg according to WO 2005/084081 and WO 2005/084082), atropisomers (eg according to WO 2006/048268) , boronic acid derivatives (eg according to WO 2006/117052) or benzanthracenes (eg according to WO 2008/145239). Particularly preferred matrix materials are selected from the class of oligoarylenes, such as naphthalenes, anthracenes, benzanthracenes and/or pyrenes or the atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides and sulfoxides. Very particularly preferred matrix materials are selected from the class of oligoarylenes, such as anthracenes, benzanthracenes, benzophenanthrenes and/or pyrenes or the atropisomers of these compounds. Oligoarylene in the meaning of the present invention is intended to mean a compound in which three or more aryl or arylene groups are bonded to each other. Also anthracene derivatives and EPs disclosed in WO 2006/097208, WO 2006/131192, WO 2007/065550, WO 2007/110129, WO 2007/065678, WO 2008/145239, WO 2009/100925, WO 2011/054442 and EP 1553154 Preference is given to the pyrene compounds disclosed in 1749809, EP 1905754 and US 2012/0187826.

Preferred matrix materials for phosphorescent emitting compounds are, in addition to the compounds of formula (I), aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones (eg WO 2004/013080, WO 2004/093207, WO 2006/005627 or according to WO 2010/006680), triarylamines, carbazole derivatives, for example CBP (N,N-biscarbazolylbiphenyl) or carbazole derivatives (WO 2005/039246, US 2005/0069729, JP 2004/ 288381, disclosed in EP 1205527 or WO 2008/086851), indolocarbazole derivatives (eg according to WO 2007/063754 or WO 2008/056746), indenocarbazole derivatives (eg according to WO 2010/136109, according to WO 2011/000455 or WO 2013/041176), azacarbazole derivatives (eg according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160), bipolar matrix materials (eg according to WO 2007/137725) silanes (eg according to WO 2005/111172), azaborol or boronic acid esters (eg according to WO 2006/117052), triazine derivatives (eg according to WO 2010/015306, WO 2007/063754) or according to WO 2008/056746), zinc complexes (eg according to EP 652273 or WO 2009/062578), diazasilol or tetraazasilol derivatives (eg according to WO 2010/054729), diazaphosphole derivatives (eg according to WO 2010/054730), bridged carbazole derivatives (eg in US 2009/0136779, WO 2010/050778, WO 2011/042107, WO 2011/088877 or WO 2012/143080 according to), triphenylene derivatives (eg in WO 2012/048781 according to), or lactams (eg according to WO 2011/116865 or WO 2011/137951).

[Y . Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials as used in this layer according to the prior art.

The OLED according to the invention preferably comprises at least two different hole-transporting layers. The compounds of formula (I) may be employed in one or some or all of the hole-transporting layers. According to a preferred embodiment, the compound of formula (I) is used in precisely one hole-transporting layer, and another compound, preferably an aromatic amine compound, is used in the other hole-transporting layer present.

Materials that can be used for the electron-transport layer are all materials as used according to the prior art as electron-transport material in the electron-transport layer. Particularly suitable are aluminum complexes such as Alq ₃ , zirconium complexes such as Zrq ₄ , lithium complexes such as Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives and phosphine oxide derivatives. Further suitable materials are derivatives of the aforementioned compounds, as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300.

The cathode of the electronic device is preferably a metal, metal alloy or various metal having a low work function, such as an alkaline earth metal, an alkali metal, a main group metal or a lanthanide (eg Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys comprising an alkali or alkaline earth metal and silver, for example alloys comprising magnesium and silver. In the case of multilayer structures, additional metals with a relatively high work function, for example Ag or Al, can also be used in addition to these metals, in which case combinations of metals, for example Ca/Ag, Mg/Ag or Ag/Ag is generally used. It may also be desirable to introduce a thin interlayer of a material having a high dielectric constant between the metallic cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal fluorides or alkaline earth metal fluorides as well as the corresponding oxides or carbonates (eg LiF, Li ₂ O, BaF ₂ , MgO, NaF, CsF, Cs ₂ CO ₃ ). etc) is. Lithium quinolinate (LiQ) can also be used for this purpose. The layer thickness of the layer is preferably between 0.5 and 5 nm.

The anode preferably comprises a material having a high work function. The anode preferably has a work function of greater than 4.5 eV compared to vacuum. Suitable for this purpose are, on the one hand, metals having a high redox potential, for example Ag, Pt or Au. On the other hand, metal/metal oxide electrodes (eg Al/Ni/NiO _x , Al/PtO _x ) may also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent to facilitate irradiation of organic materials (organic solar cells) or coupling-out of light (OLED, O-laser). . A preferred anode material here is a conductive mixed metal oxide. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is also given to conductive doped organic materials, in particular conductive doped polymers. In addition, the anode may also consist of a plurality of layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

The device is properly structured (depending on the application) provided with contacts and finally sealed and structured, thereby precluding the harmful effects of water and air.

In a preferred embodiment, the electronic device according to the invention is characterized in that at least one layer is applied by a sublimation method, wherein the material is vacuum sublimated at an initial pressure of less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar. Applied by vapor deposition in the device. However, here also the initial pressure can be much lower, for example less than 10 ^-7 mbar.

Likewise, preference is given to electronic devices characterized in that one or more layers are applied by means of the OVPD (organic vapor deposition) method or by carrier-gas sublimation, wherein the material is applied at a pressure of 10 ^-5 mbar to 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, where the material is structured by being applied directly through a nozzle (eg, MS Arnold et al. , Appl. Phys. Lett. 2008 , 92 , 053301). .

Also, for example by spin coating, or by any desired printing method, for example screen printing, flexographic printing, nozzle printing or offset printing, but particularly preferably LITI (light induction) Preference is given to electronic devices characterized in that one or more layers are prepared from solution by means of thermal imaging, thermal transfer printing) or inkjet printing. Soluble compounds of formula (1) are needed for this purpose. High solubility can be achieved through suitable substitution of the compounds.

For the production of the electronic device according to the invention, it is also preferred to apply at least one layer from solution and at least one layer by a sublimation method.

According to the invention, electronic devices comprising at least one compound of formula (I) can be used in displays, as light sources in lighting applications and as light sources in medical and/or cosmetic applications (eg light therapy). can

working example

A) Synthesis example

A-1) Synthesis of symmetric basic structures

Step 1:

100 g (0.5 mol) of 10H-acridin-9-one, 140 g (0.6 mol) of 4-bromobiphenyl, 9.6 g (0.05 mol) of CuI, 104.0 g (0.75 mol) of calcium carbonate and 22.0 ml (0.1 mol) of 2,2,6,6-tetramethylheptane-3,5-dione is dissolved in 600 ml of dimethylformamide under a protective atmosphere. The reaction mixture is heated to boiling under a protective atmosphere for 48 hours. Then water is added to the mixture. The solid is filtered off with suction, washed with water and ethanol and recrystallized from toluene.

Yield: 167 g (0.48 mol), 96% of theory.

The following compounds can be obtained analogously:

Step 2:

N -Bromosuccinimide (31.05 g, 172.7 mmol) was added in portions to a solution of dihydroacridone (30.0 g, 86.3 mmol) in DMF (1400 ml) at 0° C. while blocking light, and the mixture was stirred at room temperature overnight Stir. Half of the solvent is removed on a rotary evaporator and 300 ml of ethanol are added to the mixture. The solid is filtered off with suction and recrystallized from DMF. Yield: 42 g, 97% of theory, yellow solid.

Step 3:

21.4 g (171.7 mmol) of phenylboronic acid, 46.3 g (85.8 mmol) of dibromo-10H-acridin-9-one and 1.4 g (1.9 mmol) of Pd(PPh ₃ ) ₄ were mixed with 930 ml of di Suspended in oxane. 85.8 ml of 2M potassium carbonate solution are slowly added to the suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel and then evaporated to dryness. The residue is recrystallized from toluene/heptane.

Yield: 43 g (81 mmol), 94% of theory, purity according to GC > 94%.

A-2) Synthesis of asymmetric acridinone

Step 1:

50 g (155.5 mmol) of bisbiphenyl-4-ylamine, 66.9 g (311.1 mmol) of methyl potassium dicarbonate benzoate, 21.5 g (155.5 mmol) of potassium carbonate, 22.1 g (155.5 mmol) of sodium sulfate and 0.9 g (15.5 mmol) of copper powder are suspended in 210 ml of nitrobenzene. The reaction mixture is heated at 220° C. for 6 hours. After cooling, the mixture is filtered through celite and nitrobenzene is distilled off. The residue is filtered through silica gel (heptane/dichloromethane 1:1). The product is obtained in solid form. The yield is 64 g (91% of theory).

Step 2:

114.2 g (2722 mmol) of LiOH*H ₂ O are added to a solution of 62 g (136.1 mmol) of methyl benzoate in 294 ml of dioxane and 294 ml of water. The reaction mixture is heated at 105° C. for 16 hours. After cooling, ethyl acetate is added, and the mixture is added to 1500 ml of a 10% citric acid solution and extracted with ethyl acetate. The combined organic phases are dried and evaporated in vacuo. The residue is used in the next step without further purification.

Step 3:

62 g (140 mmol) of benzoic acid are dissolved in 364 ml of methanesulfonic acid, and the mixture is stirred at 60° C. overnight. After cooling, the mixture is slowly added to ice/water and the solid that precipitates is filtered off with suction. The solid is dissolved in ethyl acetate and washed with 20% sodium hydrogen carbonate solution. The combined organic phases are dried and evaporated in vacuo. The residue is recrystallized from MeOH. The yield is 56 g (94% of theory).

A-3) Synthesis of diarylamino intermediate

DPE-Phos (3.3 g, 6.2 mmol), palladium acetate (0.7 g, 3.1 mmol) and sodium tert-butoxide (41.5 g, 432 mmol) in degassed toluene (590 ml) with 2-bromo-4-chloro -1-iodobenzene (50 g, 154 mmol) and 4-chlorophenylamine (19.7 g, 154 mmol), and the mixture is heated under reflux for 20 h. The reaction mixture is cooled to room temperature, expanded with toluene and filtered through Celite. The filtrate is expanded with water, extracted with toluene and the combined organic phases are dried and evaporated in vacuo. The residue is filtered through silica gel (heptane). The product is obtained in the form of a pale red solid. The yield is 31 g (63% of theory).

A-4) Synthesis of spiro units

34.7 g (140 mmol) of 2-bromodiphenylamine are initially introduced into 350 ml of absolute THF cooled to -78°C, and 112 ml (280 mmol) of 2.5 M n-BuLi in THF are added. The mixture is then thawed to −10° C. and stirred at this temperature for an additional 1 h. 30 g (86 mmol) of 10-biphenyl-4-yl-2,7-diphenyl-10H-acridin-9-one dissolved in 600 ml of THF are slowly added. Then the mixture is stirred at room temperature for an additional 24 h. 100 ml of ammonium chloride solution are added, stirring is continued briefly, the organic phase is separated off and the solvent is removed in vacuo. The residue is suspended in 750 ml of warm glacial acetic acid at 40° C., 60 ml of concentrated hydrochloric acid are added to the suspension, and the mixture is then stirred for a further 8 hours at room temperature. After cooling, the precipitated solid is filtered off with suction, washed once each time with 100 ml of water and 3 times with 100 ml of ethanol and finally recrystallized from heptane. Yield: 35.3 g (54 mmol), 77% of theory.

A-5) Suzuki reaction

5.4 g (44.3 mmol) of benzeneboronic acid, 18 g (29.5 mmol) of 10-biphenyl-4-yl-2-chloro-9,9-dimethyl-9,10-dihydroacridine and 8.9 g (59.1 mmol) of CsF is suspended in 250 ml of dioxane. 1.1 g (1.5 mmol) of PdCl ₂ (PCy ₃ ) ₂ are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the mixture is filtered through silica gel, washed 3 times with 200 ml of water and evaporated to dryness. The residue is filtered through silica gel (heptane/ethyl acetate). The product is obtained in solid form. The yield is 19 g (98% of theory).

A-6) Buchwald reaction

A degassed suspension of 11.1 g (46.7 mmol) of 4-bromobiphenyl, 24.9 g (46.7 mmol) of spirobisacridine and 11.9 g (121.3 mmol) of NaO t Bu in 480 ml of toluene with N ₂ 1 Saturate for hours. Then, 1.07 g (1.9 mmol) of DPPF and 1.38 g (1.9 mmol) of palladium(II) acetate are added. The reaction mixture is heated at reflux overnight. After cooling, the organic phase is filtered through silica gel and then evaporated to dryness. The residue is recrystallized from toluene/heptane. Yield: 15.7 g (47% of theory).

B) device example

OLEDs according to the invention and OLEDs according to the prior art are produced by a general method according to WO 04/058911 which is adapted (eg material) according to the circumstances described here.

Data for various OLEDs are shown in Examples E1 to E16 and Reference Examples V1 to V4 according to the present invention. The substrate used was a glass plate coated with structured ITO (indium tin oxide) to a thickness of 50 nm. The OLED has the following layer structure: substrate / p-doped hole-injection layer (HIL) / hole-transport layer (HTL) / optionally p-doped hole-transport layer / electron-blocking layer (EBL) / emissive layer (EML) / electron-transport layer (ETL) / electron-injection layer (EIL) and finally the cathode. The cathode is formed by an aluminum layer having a thickness of 100 nm.

Materials required for OLED production are shown in Table 1, and various component structures are shown in Table 2.

All materials are applied by thermal evaporation in a vacuum chamber. The emissive layer here always consists of at least one matrix material (host material) and an emissive dopant (emitter), which are admixed with the matrix material(s) by co-evaporation in a specific volume ratio. An expression such as H1:SEB (95%:5%) here means that material H1 is present in the layer in a volume ratio of 95% and SEB is present in the layer in a volume ratio of 5%. Similarly, the electron-transporting layer or hole-injecting layer may also consist of a mixture of two or more materials.

OLEDs are analyzed by standard methods. For this purpose, the electroluminescence spectrum as a function of the luminescence density and the current efficiency (cd/A), the power, calculated from the current/voltage/luminescence density characteristic line (IUL characteristic line) estimating the Lambert radiation characteristic. Efficiency and external quantum efficiency (EQE, %), and lifetime are measured. The expression EQE @ 10 mA/cm ² represents the external quantum efficiency at a current density of 10 mA/cm ² . LT80 @ 60 mA/cm ² is the lifetime at which the OLED drops to 80% of its initial strength at a constant current of 60 mA/cm ² .

Table 1. Structure of the materials used

Table 2. Structure of OLED

Example 1

In example 1, a material according to the invention (HTM5) and a material of the prior art (HTMV2) are compared in an OLED comprising a blue-fluorescence emitting layer. The compounds are each used in the hole-transporting layer of the OLED.

The external quantum efficiency at 10 mA/cm ² of the compound according to the invention from 8.5% of sample E1 is significantly better than that of only 6.0% of the reference sample V1. The lifetime LT80 at 60 mA/cm ² is significantly increased to 115 hours for sample E1 according to the invention compared to the prior art at V1 of 38 hours.

The two substances are likewise compared in the triplet green component. Reference sample V2 shows a significantly lower quantum efficiency of 16.3% at 2 mA/cm ² than sample E2 according to the invention of 20.1%. The lifetime LT80, 223 hours, of sample E2 according to the invention is significantly longer than the reference lifetime of V2 of 96 hours.

Example 2

In Example 2, four additional substances according to the invention (HTM1, HTM2, HTM3 and HTM4) are compared with the prior art (HTMV1).

In the singlet blue component, sample E3 according to the invention achieves a higher quantum efficiency of 9.8% at 10 mA/cm ² than the prior art (V3) of 8.5%. The lifetime (80%) of the components comprising the materials E3-E6 according to the invention, E3 (214 hours), E4 (180 hours), E5 (154 hours) and E6 (166 hours) is that of the comparative material (V3) Lifespan significantly longer than 66 hours.

In the triplet green component, the reference sample V4 (19.8%) shows a lower quantum efficiency at 2 mA/cm ² than for example sample E10 according to the invention (20.4%). The lifetime (80%) at 20 mA/cm ² of samples E10 (199 h), E11 (223 h), E12 (205 h) and E13 (214 h) according to the invention is also only 193 h prior art V4 longer than in the case of

Example 3

In Example 3, three additional substances according to the invention (HTM6, HTM7 and HTM8) are compared with the prior art (HTMV1).

In the singlet blue component, samples E8 and E9 according to the invention achieve higher quantum efficiencies of 8.6% and 9.1% respectively at 10 mA/cm ² than the prior art (V3) of 8.5%. The lifetime (80%) of the component comprising material E8 according to the invention of 150 hours is significantly longer than that of the comparative component V3 of 66 hours.

In the triplet green component, reference sample V4 (19.8%) shows a lower quantum efficiency at 2 mA/cm ² than samples E14 (21.5%), E15 (20.2%) and E16 (20.6%) according to the invention.

Claims (20)

A compound of formula (I):

[wherein the following applies to the symbols and exponents used:
A is C;
Y is N;
X is CR ¹ ;
Ar ¹ , Ar ² are in each case identically or differently an aromatic ring system having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R ² , or 5 to 24 aromatic ring atoms heteroaromatic ring systems, which may be substituted by one or more radicals R ² ;
Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ in each case, identically or differently, are aromatic ring systems having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R ² , or 5 to 24 heteroaromatic ring systems having two aromatic ring atoms, which may be substituted by one or more radicals R ² ;
R ¹ in each occurrence, identically or differently, is H, F, CN, Si(R ³ ) ₃ , an aromatic ring system having 6 to 24 aromatic ring atoms and a heteroaromatic ring system having 5 to 24 aromatic ring atoms is selected from; wherein said aromatic ring system and said heteroaromatic ring system may each be substituted by one or more radicals R ³ ;
R ² in each occurrence, identically or differently, is H, F, CN, Si(R ³ ) ₃ , a straight chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms, an aromatic ring system having 6 to 24 aromatic ring atoms and a heteroaromatic ring system having 5 to 24 aromatic ring atoms; wherein the alkyl group, the aromatic ring system and the heteroaromatic ring system may each be substituted by one or more radicals R ³ ;
R ³ is at each occurrence, identically or differently, H, F, CN, Si(R ⁴ ) ₃ , a straight chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms, an aromatic ring system having 6 to 24 aromatic ring atoms and a heteroaromatic ring system having 5 to 24 aromatic ring atoms; wherein the alkyl group, the aromatic ring system and the heteroaromatic ring system may each be substituted by one or more radicals R ⁴ ;
R ⁴ in each occurrence, identically or differently, represents H, D, F, CN, an alkyl group having 1 to 20 C atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and 5 to 40 aromatic ring atoms selected from heteroaromatic ring systems having; wherein two or more radicals R ⁴ may be linked to each other and may form a ring; wherein the alkyl group, aromatic ring system and heteroaromatic ring system may be substituted with F or CN;
a, b, c, d are at each occurrence, identically or differently, 0 or 1;
At least one of the two groups Ar ¹ and Ar ² is an aromatic ring system having 12 to 24 aromatic ring atoms, which may be substituted by one or more radicals R ² , or heteroaromatic having 12 to 24 aromatic ring atoms is a ring system, which may be substituted by one or more radicals R ² ;
at least one of the indices a, b, c and d is 1]. The compound according to claim 1, characterized in that it does not contain an arylamino group as a substituent. The compound according to claim 1, characterized in that exactly 1, 2 or 3 indices selected from the indices a, b, c and d in formula (I) are equal to 1. delete delete delete delete 2. An aromatic ring system according to claim 1, wherein both the groups Ar ¹ and Ar ² in each case, identically or differently, have from 12 to 24 aromatic ring atoms, which may be substituted by one or more radicals R ² , and A compound, characterized in that it is selected from heteroaromatic ring systems having 12 to 24 aromatic ring atoms, which may be substituted by one or more radicals R ² . The compound according to claim 1, wherein the groups Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ appearing in the compound of formula (I) are identically selected. The compound of claim 1 , wherein at least one of the groups Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ comprises at least one heteroaryl group having from 5 to 20 aromatic ring atoms. The compound according to claim 1, characterized in that the compound of formula (I) is according to one of the following formulas (I-1) to (I-3):

[wherein the symbols and exponents appearing are defined according to paragraph 1]. 12. A process for the preparation of a compound according to any one of claims 1 to 3 and 8 to 11, characterized in that it comprises the steps of:
1) reacting a halogen-substituted diphenylamine derivative with an acridinone derivative in the presence of an organometallic compound;
2) yielding a spirobisacridine derivative by ring closure reaction of the intermediate formed in 1);
3) introducing an aryl or heteroaryl group on the free nitrogen atom of the spirobisacridine derivative by Buchwald coupling. 12. An oligomer, polymer or dendrimer comprising a compound according to any one of claims 1 to 3 and 8 to 11, wherein the bond(s) to said polymer, oligomer or dendrimer is R ¹ or R ² An oligomer, polymer or dendrimer, which may be localized at any desired position in formula (I) substituted by 12. An oligomer containing a compound according to any one of claims 1 to 3 and 8 to 11, or a compound according to any one of claims 1 to 3 and 8 to 11. , an oligomer, polymer or dendrimer, which can be localized at any desired position in formula (I) wherein the bond(s) to said polymer, oligomer or dendrimer is substituted by R ¹ or R ² , and one or more solvents. 11. A compound according to any one of claims 1 to 3 and 8 to 10, characterized in that it is used in an electronic device. 12. An oligomer containing a compound according to any one of claims 1 to 3 and 8 to 10 or a compound according to any one of claims 1 to 3 and 8 to 11; as a polymer or dendrimer, comprising an oligomer, polymer or dendrimer, which may be localized at any desired position in formula (I) wherein the bond(s) to said polymer, oligomer or dendrimer is substituted by R ¹ or R ² . electronic device. 17. The method of claim 16, wherein an organic integrated circuit (OIC), an organic field effect transistor (OFET), an organic thin film transistor (OTFT), an organic light emitting transistor (OLET), an organic solar cell (OSC), an organic optical detector, an organic photoreceptor, An electronic device selected from the group consisting of organic electroluminescent devices (OFQDs), organic light emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs). 18. Electronic device according to claim 17, characterized in that the compound or oligomer, polymer or dendrimer is present in a layer selected from a hole-transporting layer and an emissive layer. 19. Electronic device according to claim 18, characterized in that compounds or oligomers, polymers or dendrimers are present in the emission layer together with at least one phosphorescent emitter. 19. Electronic device according to claim 18, characterized in that compounds or oligomers, polymers or dendrimers are present in the hole-transporting layer together with at least one p-dopant.